WO2016094179A1 - Mto haute pression avec sapo-34 à % élevé en si - Google Patents

Mto haute pression avec sapo-34 à % élevé en si Download PDF

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WO2016094179A1
WO2016094179A1 PCT/US2015/063662 US2015063662W WO2016094179A1 WO 2016094179 A1 WO2016094179 A1 WO 2016094179A1 US 2015063662 W US2015063662 W US 2015063662W WO 2016094179 A1 WO2016094179 A1 WO 2016094179A1
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stream
passing
generate
paragraph
olefins
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PCT/US2015/063662
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English (en)
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Nicholas J. SCHOENFELDT
Thulasidas Chellppannair
Wolfgang A. Spieker
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Uop Llc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1018—Biomass of animal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • the present invention relates to the conversion of oxygenates to olefins.
  • this invention relates to the conversion of methanol to light olefins.
  • Light olefins serve as feed materials for the production of numerous chemicals. Light olefins have traditionally been produced through the processes of steam or catalytic cracking. The limited availability and high cost of petroleum sources, however, has resulted in a significant increase in the cost of producing light olefins from such petroleum sources.
  • oxygenates such as alcohols and, more particularly, to the use of methanol, ethanol, and higher alcohols or their derivatives.
  • the oxygenates are often produced from more plentiful sources of raw materials, such as conversion of natural gas to alcohols, or the production of oxygenates from coal.
  • Molecular sieves such as microporous crystalline zeolite and non-zeolitic catalysts, particularly silicoalummophosphates (SAPO), are known to promote the conversion of oxygenates to hydrocarbon mixtures, particularly hydrocarbon mixtures composed largely of light olefins.
  • the amounts of light olefins resulting from such processing can be further increased by reacting, i.e., cracking, heavier hydrocarbon products, particularly heavier olefins such as C 4 and C 5 olefins, to light olefins.
  • heavier hydrocarbon products particularly heavier olefins such as C 4 and C 5 olefins
  • U.S. Patent 5,914,433 to Marker discloses a process for the production of light olefins comprising olefins having from 2 to 4 carbon atoms per molecule from an oxygenate feedstock.
  • the process comprises passing the oxygenate feedstock to an oxygenate conversion zone containing a metal aluminophosphate catalyst to produce a light olefin stream.
  • a propylene and/or mixed butylene stream is fractionated from said light olefin stream and cracked to enhance the yield of ethylene (C 2 H 4 ) and propylene (C 3 H 6 ) products.
  • This combination of light olefin product and propylene and butylene cracking in a riser cracking zone or a separate cracking zone provides flexibility to the process which overcomes the equilibrium limitations of the aluminophosphate catalyst.
  • the invention provides the advantage of extended catalyst life and greater catalyst stability in the oxygenate conversion zone.
  • the present invention provides for a process to increase the propylene yields in an oxygenate to olefins conversion process.
  • the process utilizes a high silicon molecular sieve catalyst and is operated at a high pressure.
  • a first embodiment of the invention is a process for the conversion of oxygenates to olefins, comprising passing an oxygenate feed to an oxygenate conversion reactor; and passing a high silica SAPO-34 catalyst to the oxygenate reactor, to react with the oxygenate feed to generate an effluent stream comprising olefins; wherein the reaction conditions include a high partial oxygenate pressure, wherein the oxygenate partial pressure is between 100 kPa and 2.5 MPa.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the silicon content of the SAPO-34 is at least 4%.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the silicon content of the SAPO-34 is at least 5%.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the oxygenate is methanol.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the oxygenate partial pressure is at least 100 kPa.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the oxygenate partial pressure is between 0.1 MPa and 2.5 MPa.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the effluent stream to a dewatering column to generate a dewatered effluent stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the dewatered stream to a DME recovery unit to generate a DME stream and a DME olefins stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the DME olefins stream to a light olefins recovery unit to generate an ethylene stream, a propylene stream and a heavies stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the heavies stream to an olefin cracking unit to generate an olefin cracking effluent stream comprising light olefins.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the olefin cracking effluent stream to the light olefins recovery unit.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the DME olefins stream to a light olefins recovery unit to generate an ethylene stream, a propylene stream, a butene stream and a heavies stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the butene stream to a butadiene unit to generate a butadiene effluent stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing a portion of the ethylene stream and a portion of the butene stream to a metathesis unit to generate a metathesis effluent stream comprising propylene.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the metathesis effluent stream to the light olefins recovery unit.
  • a second embodiment of the invention is a process for the conversion of oxygenates to olefins, comprising passing an oxygenate feed to a fixed bed reactor comprising an oxygenate conversion catalyst and operated at reaction conditions, to generate an effluent stream comprising olefins, wherein the reaction conditions include a high pressure, wherein the high pressure includes an oxygenate partial pressure greater than 350 kPa.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the oxygenate conversion catalyst comprises a high silica SAPO-34.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the silica content of the SAPO-34 is at least 4%.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the oxygenate conversion catalyst is SAPO-34 with at least a 5% silica content.
  • Figure 1 shows the comparative stability of SAPO-34 and SAPO-18
  • Figure 2 is a schematic of the oxygenates to olefins process.
  • the oxygenate feedstock is catalytically converted over a silicoaluminophosphate (SAPO) catalyst.
  • SAPO silicoaluminophosphate
  • the increase in light olefin production is also described in US Pat. No. 7,317,133 wherein the production of heavier olefins are directed to an olefin cracking reactor to generate a process stream comprising light olefins.
  • the olefin cracking process utilizes a different catalyst from a family of crystalline silicate having an MFI or MEL. Examples of these catalysts include ZSM-5 or ZSM-11.
  • Processes are also developed that operate around control conditions of the reactor, such as US Pat. No. 6,137,022, wherein the reaction zone is operated to contain a restricted amount of catalyst, containing 15 volume percent or less, and operation is controlled to limit conversion of the feedstock to between 80 and 99%.
  • P/E product ratio is largely determined by the MTO and OCP reactor yields.
  • a high P/E ratio, preferably more than 3 is desirable due to the increased demand for propylene. Due to this increase in demand for higher propylene over ethylene, it has been discovered that changing the catalyst preference and increasing the pressure substantially has changed not only the product ratios in the MTO process, but the catalyst deactivation rate has been found to decrease, thereby enabling longer cycle times and improved economics.
  • SAPO-34 SAPO-34
  • SAPO-18 SAPO-18
  • the process is a process for the conversion of oxygenates to olefins.
  • the process includes passing an oxygenate feed 8 to an oxygenate conversion reactor 10.
  • the oxygenate conversion reactor 10 is a fluidized bed reactor and includes a high silica SAPO-34 catalyst in the oxygenate reactor 10, to react with the oxygenate feed to generate an effluent stream 12 comprising olefins.
  • the reaction conditions include operating at a high oxygenate partial pressure wherein the oxygenate partial pressure is between 100 kPa and 2.5 MPa.
  • the fluidized bed reactor 10 passes a spent catalyst stream 14 to a regenerator 20 and returns a regenerated catalyst stream 22 to the reactor 10.
  • the process includes passing the effluent stream 12 to a dewatering column 30 to generate a dewatered effluent stream 32 and a waste water stream 34.
  • the process further includes passing the dewatered stream 32 to a compressor 40 to generate a compressed stream 42.
  • the compressed stream 42 is passed to a dimethyl ether (DME) recovery unit 50 to generate a DME stream 54 and a DME olefins stream 52.
  • the DME olefins stream 52 is passed to a light olefins recovery unit 60 to generate an ethylene stream 62, an propylene stream 64, a butylenes stream 66 and a heavies stream 68.
  • DME dimethyl ether
  • the higher pressure of the oxygenate conversion reactor 10 increases the heavier olefin content of the effluent stream 12.
  • the heavies stream 68 can be passed to an olefin cracking unit 70 to generate an olefin cracking effluent stream 72 comprising light olefins.
  • the olefins cracking effluent stream 72 can be passed to a separation unit 80 for removing residual heavies 82, and generating a light olefin stream 84 for passage to the light olefins recovery unit 60.
  • the butylenes stream 66 can be passed to an on-purpose butadiene (OPBD) unit for the conversion of butenes to butadienes.
  • the process can further include passing a portion of the ethylene stream 62 and a portion, or all, of the butylenes stream 66 to a metathesis unit 90 to generate a metathesis effluent stream 92 comprising propylene.
  • the metathesis effluent stream 92 can be directed to the light olefins recovery unit 60 to separate the propylene from other metathesis by products.
  • the process is operated wherein the oxygenate partial pressure at the inlet is at least 100 kPa, with a preferred partial pressure at the inlet of at least 200 kPa. A more preferred partial pressure at the inlet is between 200 kPa and 1.7 MPa.
  • the oxygenates can include alcohols and ethers, and a preferred oxygenate is methanol.
  • reaction temperatures for the MTO process include temperatures between 350°C and 500°C, with a preferred value around 375°C to 475°C.
  • the methanol to olefins (MTO) conversion process operates at a low pressure, wherein the inlet partial pressure of the methanol is on the order 40 kPa (6 psi).
  • MTO methanol to olefins
  • a commercial catalyst for MTO is SAPO-34.
  • SAPO-34 As the pressure increases, the catalyst has been found to more rapidly deactivate.
  • the preferred catalyst is a SAPO-34 with at least 4% silicon, with a more preferred content of 5% silicon.
  • the silicon content of the catalyst is the percent of the Si atoms out of the total of silicon, aluminum and phosphorus atoms that form the molecular sieve.
  • the Table shows the results for comparing a low silicon SAPO with a higher silicon SAPO.
  • the runs were at elevated pressures and temperature of 400C and 435C.
  • the results show a shift in the production of olefins with a decrease in the amount of ethylene while increasing the propylene and butylene content in the MTO reactor effluent streams.
  • a first embodiment of the invention is a process for the production of light olefins from an oxygenate feed, comprising passing the oxygenate feed to an MTO reactor, wherein the reactor comprises an MTO catalyst comprising a silicoaluminophosphate, and is operated at reaction conditions to generate an effluent stream comprising olefins with a desired ratio of ethylene, propylene, and butylenes.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the MTO reactor is a fluidized bed.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the silicoaluminophosphate is SAPO-18, SAPO-34, SAPO-5 or combinations thereof.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the silicoaluminophosphate is SAPO-34.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the SAPO-34 catalyst contains a Si-content of between 3-7 %, such as between 3.5- 6.5 %, such as between 3.5-5%.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the oxygenates comprise alcohols, aldehydes and ethers.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the oxygenate comprises methanol and dimethyl ether.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the oxygenate comprises methanol.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the process pressure and temperature are set to provide a desired butylenes to ethylene ratio.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the inlet partial pressure of the oxygenate is between 0.1 and 2.5 MPa, and preferably between 0.2MPa and 2. MPa.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the process temperature is between 300°C and 500°C, or more preferably between 375°C and 475°C.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the effluent stream to a light olefins recovery unit.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the effluent stream to a quench tower to generate a water stream and a dewatered effluent stream; passing the dewatered effluent stream to a compressor to generate a compressed stream; passing the compressed stream to a DME recovery unit to generate a DME stream and a DME olefins stream; and passing the DME olefins stream to a light olefins recovery unit to generate an ethylene stream, a propylene stream and a C4+ heavies stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the heavies stream to an olefin cracking unit to generate an olefins cracking effluent stream comprising light olefins.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the olefins cracking effluent stream to the light olefins recovery unit.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the effluent stream to a quench tower to generate a water stream and a dewatered effluent stream; passing the dewatered effluent stream to a compressor to generate a compressed stream; passing the compressed stream to a DME recovery unit to generate a DME stream and a DME olefins stream; and passing the DME olefins stream to a light olefins recovery unit to generate an ethylene stream, a propylene stream, a C4 olefin stream and a C5+ heavies stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing a portion or substantially all of the C4 olefin product stream and a portion or substantially all of the ethylene product stream to a metathesis reactor, thereby generating a metathesis stream comprising mostly of propylene.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the C5+ heavies stream to an olefin cracking unit to generate an olefins cracking effluent stream comprising light olefins.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the olefins cracking effluent stream to the light olefins recovery unit.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the effluent stream to a quench tower to generate a water stream and a dewatered effluent stream; passing the dewatered effluent stream to a compressor to generate a compressed stream; passing the compressed stream to a DME recovery unit to generate a DME stream and a DME olefins stream; and passing the DME olefins stream to a light olefins recovery unit to generate an ethylene stream, a propylene stream, a C4 olefin stream, a C5 olefin stream and a C6+ heavies stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing a portion or substantially all of the C5 product stream and a portion or substantially all of the ethylene product stream to a metathesis reactor, thereby generating a metathesis stream comprising mostly of propylene and butenes.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the C4 product stream to a C4 separation unit to generate an isobutene stream and normal butene stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the normal butene stream to an oxidative dehydrogenation reactor, thereby generating an on purpose butadiene stream consisting of butadiene.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the C6+ heavies stream to an olefin cracking unit to generate an olefins cracking effluent stream comprising light olefins.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the olefins cracking effluent stream to the light olefins recovery unit.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the effluent stream to a quench tower to generate a water stream and a dewatered effluent stream; passing the dewatered effluent stream to a compressor to generate a compressed stream; passing the compressed stream to a DME recovery unit to generate a DME stream and a DME olefins stream; and passing the DME olefins stream to a light olefins recovery unit to generate an ethylene stream, a propylene stream, a C4 olefin stream, a C5 product stream and a C6+ heavies stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing a portion or substantially all of the C5 heavy stream and a portion or substantially all of the ethylene product stream to a metathesis reactor, thereby generating a metathesis stream comprising mostly of propylene and butenes.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the C4 product stream to a C4 separation unit to generate an isobutene stream and normal butene stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the C6+ heavies stream to an olefin cracking unit to generate an olefins cracking effluent stream comprising light olefins.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the olefins cracking effluent stream to the light olefins recovery unit.
  • a first embodiment of the invention is a process for the production of light olefins from an oxygenate feed, comprising passing the oxygenate feed to an MTO reactor, wherein the reactor comprises an MTO catalyst comprising a silicoaluminophosphate, and is operated at reaction conditions to generate an effluent stream comprising olefins with a desired ratio of ethylene, propylene, and butylenes.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the MTO reactor is a fluidized bed.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the silicoaluminophosphate is SAPO-18, SAPO-34, SAPO-5 or combinations thereof.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the silicoaluminophosphate is SAPO-34.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the SAPO-34 catalyst contains a Si-content of between 3-7 %, such as between 3.5- 6.5 %, such as between 3.5-5%.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the oxygenates comprise alcohols, aldehydes and ethers.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the oxygenate comprises methanol and dimethyl ether.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the oxygenate comprises methanol.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the process pressure and temperature are set to provide a desired butylenes to ethylene ratio.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the inlet partial pressure of the oxygenate is between 0.1 and 2.5 MPa, and preferably between 0.2MPa and 2. MPa.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the process temperature is between 300°C and 500°C, or more preferably between 375°C and 475°C.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the effluent stream to a light olefins recovery unit.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the effluent stream to a quench tower to generate a water stream and a dewatered effluent stream; passing the dewatered effluent stream to a compressor to generate a compressed stream; passing the compressed stream to a DME recovery unit to generate a DME stream and a DME olefins stream; and passing the DME olefins stream to a light olefins recovery unit to generate an ethylene stream, a propylene stream and a C4+ heavies stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the heavies stream to an olefin cracking unit to generate an olefins cracking effluent stream comprising light olefins.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the olefins cracking effluent stream to the light olefins recovery unit.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the effluent stream to a quench tower to generate a water stream and a dewatered effluent stream; passing the dewatered effluent stream to a compressor to generate a compressed stream; passing the compressed stream to a DME recovery unit to generate a DME stream and a DME olefins stream; and passing the DME olefins stream to a light olefins recovery unit to generate an ethylene stream, a propylene stream, a C4 olefin stream and a C5+ heavies stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing a portion or substantially all of the C4 olefin product stream and a portion or substantially all of the ethylene product stream to a metathesis reactor, thereby generating a metathesis stream comprising mostly of propylene.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the C5+ heavies stream to an olefin cracking unit to generate an olefins cracking effluent stream comprising light olefins.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the olefins cracking effluent stream to the light olefins recovery unit.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the effluent stream to a quench tower to generate a water stream and a dewatered effluent stream; passing the dewatered effluent stream to a compressor to generate a compressed stream; passing the compressed stream to a DME recovery unit to generate a DME stream and a DME olefins stream; and passing the DME olefins stream to a light olefins recovery unit to generate an ethylene stream, a propylene stream, a C4 olefin stream, a C5 olefin stream and a C6+ heavies stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing a portion or substantially all of the C5 product stream and a portion or substantially all of the ethylene product stream to a metathesis reactor, thereby generating a metathesis stream comprising mostly of propylene and butenes.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the C4 product stream to a C4 separation unit to generate an isobutene stream and normal butene stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the normal butene stream to an oxidative dehydrogenation reactor, thereby generating an on purpose butadiene stream consisting of butadiene.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the C6+ heavies stream to an olefin cracking unit to generate an olefins cracking effluent stream comprising light olefins.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the olefins cracking effluent stream to the light olefins recovery unit.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the effluent stream to a quench tower to generate a water stream and a dewatered effluent stream; passing the dewatered effluent stream to a compressor to generate a compressed stream; passing the compressed stream to a DME recovery unit to generate a DME stream and a DME olefins stream; and passing the DME olefins stream to a light olefins recovery unit to generate an ethylene stream, a propylene stream, a C4 olefin stream, a C5 product stream and a C6+ heavies stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing a portion or substantially all of the C5 heavy stream and a portion or substantially all of the ethylene product stream to a metathesis reactor, thereby generating a metathesis stream comprising mostly of propylene and butenes.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the C4 product stream to a C4 separation unit to generate an isobutene stream and normal butene stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the C6+ heavies stream to an olefin cracking unit to generate an olefins cracking effluent stream comprising light olefins.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the olefins cracking effluent stream to the light olefins recovery unit.

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  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de conversion de composés oxygénés en oléfines. Le procédé consiste à faire fonctionner un réacteur de conversion de composés oxygénés en oléfines à une pression élevée. Le procédé comprend également l'utilisation d'un catalyseur à tamis moléculaire du type SAPO ayant une teneur élevée en silicium. Le procédé génère une teneur supérieure en propylène, et une augmentation de la teneur des constituants plus lourds pour le traitement en aval.
PCT/US2015/063662 2014-12-11 2015-12-03 Mto haute pression avec sapo-34 à % élevé en si WO2016094179A1 (fr)

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CN107952477A (zh) * 2016-10-14 2018-04-24 中国石油化工股份有限公司 多级孔sapo分子筛在甲醇制烯烃反应中的应用

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SU1115403A1 (ru) * 1982-11-24 1999-10-20 С.М. Комаров Способ получения бутадиена
WO2008076675A1 (fr) * 2006-12-21 2008-06-26 Uop Llc Conversion d'oxygénat en oléfines avec métathèse
WO2010081705A1 (fr) * 2009-01-13 2010-07-22 Saipem. S.P.A. Procédé pour l'obtention de 1-butène de haute pureté à partir de mélanges d'hydrocarbures en c4
US8373013B2 (en) * 2006-07-13 2013-02-12 China Petroleum & Chemical Corporation Process for combining the catalytic conversion of organic oxygenates and the catalytic conversion of hydrocarbons
CN103058811A (zh) * 2011-10-24 2013-04-24 中国石油化工股份有限公司 流化床催化裂解制烯烃的方法
US8603431B2 (en) * 2007-07-06 2013-12-10 Casale Chemicals S.A. Process for preparing silicoaluminophosphate (SAPO) molecular sieves, catalysts containing said sieves and catalytic dehydration processes using said catalysts

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Publication number Priority date Publication date Assignee Title
SU1115403A1 (ru) * 1982-11-24 1999-10-20 С.М. Комаров Способ получения бутадиена
US8373013B2 (en) * 2006-07-13 2013-02-12 China Petroleum & Chemical Corporation Process for combining the catalytic conversion of organic oxygenates and the catalytic conversion of hydrocarbons
WO2008076675A1 (fr) * 2006-12-21 2008-06-26 Uop Llc Conversion d'oxygénat en oléfines avec métathèse
US8603431B2 (en) * 2007-07-06 2013-12-10 Casale Chemicals S.A. Process for preparing silicoaluminophosphate (SAPO) molecular sieves, catalysts containing said sieves and catalytic dehydration processes using said catalysts
WO2010081705A1 (fr) * 2009-01-13 2010-07-22 Saipem. S.P.A. Procédé pour l'obtention de 1-butène de haute pureté à partir de mélanges d'hydrocarbures en c4
CN103058811A (zh) * 2011-10-24 2013-04-24 中国石油化工股份有限公司 流化床催化裂解制烯烃的方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107952477A (zh) * 2016-10-14 2018-04-24 中国石油化工股份有限公司 多级孔sapo分子筛在甲醇制烯烃反应中的应用
CN107952477B (zh) * 2016-10-14 2020-09-04 中国石油化工股份有限公司 多级孔sapo分子筛在甲醇制烯烃反应中的应用

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